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Antisolvent-assisted spin coating has been widely used for fabricating metal halide perovskite films with smooth and compact morphology. However, localized nanoscale inhomogeneities exist in these films owing to rapid crystallization, undermining their overall optoelectronic performance. Here, we show that by relaxing the requirement for film smoothness, outstanding film quality can be obtained simply through a post-annealing grain growth process without passivation agents. The morphological changes, driven by a vaporized methylammonium chloride (MACl)-dimethylformamide (DMF) solution, lead to comprehensive defect elimination. Our nanoscale characterization visualizes the local defective clusters in the as-deposited film and their elimination following treatment, which couples with the observation of emissive grain boundaries and excellent inter- and intragrain optoelectronic uniformity in the polycrystalline film. Overcoming these performance-limiting inhomogeneities results in the enhancement of the photoresponse to low-light (<0.1 mW cm-2) illumination by up to 40-fold, yielding high-performance photodiodes with superior low-light detection.
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A large amount of research within organic biosensors is dominated by organic electrochemical transistors (OECTs) that use conducting polymers such as poly(3,4-ethylene dioxythiophene) doped with poly(styrenesulfonate) (PEDOT:PSS). Despite the recent advances in OECT-based biosensors, the sensing is solely reliant on the amperometric detection of the bioanalytes. This is typically accompanied by large undesirable parasitic electrical signals from the electroactive components in the electrolyte. Herein, we present the use of in situ resonance Raman spectroscopy to probe subtle molecular structural changes of PEDOT:PSS associated with its doping level. We demonstrate how such doping level changes of PEDOT:PSS can be used, for the first time, on operational OECTs for sensitive and selective metabolite sensing while simultaneously performing amperometric detection of the analyte. We test the sensitivity by molecularly sensing a lowest glucose concentration of 0.02 mM in phosphate-buffered saline solution. By changing the electrolyte to cell culture media, the selectivity of in situ resonance Raman spectroscopy is emphasized as it remains unaffected by other electroactive components in the electrolyte. The application of this molecular structural probe highlights the importance of developing biosensing probes that benefit from high sensitivity of the material's structural and electrical properties while being complimentary with the electronic methods of detection.
Assuntos
Técnicas Biossensoriais/instrumentação , Compostos Bicíclicos Heterocíclicos com Pontes/química , Sondas Moleculares/química , Polímeros/química , Poliestirenos/química , Biotecnologia , Meios de Cultura/análise , Meios de Cultura/metabolismo , Desenho de Equipamento , Glucose/análise , Glucose Oxidase/química , Glucose Oxidase/metabolismoRESUMO
The microstructure of the active blend layer has been shown to be a critically important factor in the performance of organic solar devices. Block copolymers provide a potentially interesting avenue for controlling this active layer microstructure in solar cell blends. Here we explore the impact of backbone fluorination in block copolymers of poly(3-octyl-4-fluorothiophene)s and poly(3-octylthiophene) (F-P3OT-b-P3OT). Two block co-polymers with varying block lengths were prepared via sequential monomer addition under Kumada catalyst transfer polymerisation (KCTP) conditions. We compare the behavior of the block copolymer to that of the corresponding homopolymer blends. In both types of system, we find the fluorinated segments tend to dominate the UV-visible absorption and molecular vibrational spectral features, as well as the thermal behavior. In the block copolymer case, non-fluorinated segments appear to slightly frustrate the aggregation of the more fluorinated block. However, in situ temperature dependent Raman spectroscopy shows that the intramolecular order is more thermally stable in the block copolymer than in the corresponding blend, suggesting that such materials may be interesting for enhanced thermal stability of organic photovoltaic active layers based on similar systems.
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We report two strategies toward the synthesis of 3-alkyl-4-fluorothiophenes containing straight (hexyl and octyl) and branched (2-ethylhexyl) alkyl groups. We demonstrate that treatment of the dibrominated monomer with 1 equiv of alkyl Grignard reagent leads to the formation of a single regioisomer as a result of the pronounced directing effect of the fluorine group. Polymerization of the resulting species affords highly regioregular poly(3-alkyl-4-fluoro)thiophenes. Comparison of their properties to those of the analogous non-fluorinated polymers shows that backbone fluorination leads to an increase in the polymer ionization potential without a significant change in optical band gap. Fluorination also results in an enhanced tendency to aggregate in solution, which is ascribed to a more co-planar backbone on the basis of Raman and DFT calculations. Average charge carrier mobilities in field-effect transistors are found to increase by up to a factor of 5 for the fluorinated polymers.
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We report on the electrochemical stability of hole polarons in three conjugated polymers probed by resonant Raman spectroscopy. The materials considered are all isostructural to poly(3-hexyl)thiophene, where thiazole units have been included to systematically deepen the energy level of the highest occupied molecular orbital (HOMO). We demonstrate that increasing the thiazole content planarizes the main conjugated backbone of the polymer and improves the electrochemical stability in the ground state. However, these more planar thiazole containing polymers are increasingly susceptible to electrochemical degradation in the polaronic excited state. We identify the degradation mechanism, which targets the C=N bond in the thiazole units and results in disruption of the main polymer backbone conjugation. The introduction of thiazole units to deepen the HOMO energy level and increase the conjugated backbone planarity can be beneficial for the performance of certain optoelectronic devices, but the reduced electrochemical stability of the hole polaron may compromise their operational stability.
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We report a detailed characterization of the thin film morphology of all-polymer blend devices by applying a combined analysis of physical, chemical, optical, and charge transport properties. This is exemplified by considering a model system comprising poly(3-hexylthiophene) (P3HT) and poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT). We show that the interactions between the two conjugated polymer components can be controlled by pre-forming the P3HT into highly ordered nanowire structures prior to blending with F8BT, and by varying the molecular weight of the F8BT. As a result, it is possible to produce films containing highly ordered P3HT with hole mobilities enhanced by three orders of magnitude over the pristine blends. Raman spectroscopy under resonant excitation conditions is used to probe the molecular order of both P3HT and F8BT phases within the blend films and these morphological studies are complemented by measurements of photocurrent generation. The resultant increase in photocurrent is associated with the enhanced charge carrier mobilities. The complementary analytical method demonstrated here is applicable to a wide range of polymer blend systems for all applications where the relationships between morphology and device performance are of interest.
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The fabrication process for the uniform large-scale MoS2, WS2 transition-metal dichalcogenides (TMDCs) monolayers, and their heterostructures has been developed by van der Waals epitaxy (VdWE) through the reaction of MoCl5 or WCl6 precursors and the reactive gas H2S to form MoS2 or WS2 monolayers, respectively. The heterostructures of MoS2/WS2 or WS2/MoS2 can be easily achieved by changing the precursor from WCl6 to MoCl5 once the WS2 monolayer has been fabricated or switching the precursor from MoCl5 to WCl6 after the MoS2 monolayer has been deposited on the substrate. These VdWE-grown MoS2, WS2 monolayers, and their heterostructures have been successfully deposited on Si wafers with 300 nm SiO2 coating (300 nm SiO2/Si), quartz glass, fused silica, and sapphire substrates using the protocol that we have developed. We have characterized these TMDCs materials with a range of tools/techniques including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), micro-Raman analysis, photoluminescence (PL), atomic force microscopy (AFM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and selected-area electron diffraction (SAED). The band alignment and large-scale uniformity of MoS2/WS2 heterostructures have also been evaluated with PL spectroscopy. This process and resulting large-scale MoS2, WS2 monolayers, and their heterostructures have demonstrated promising solutions for the applications in next-generation nanoelectronics, nanophotonics, and quantum technology.
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The operational stability of organic-inorganic halide perovskite based solar cells is a challenge for widespread commercial adoption. The mobility of ionic species is a key contributor to perovskite instability since ion migration can lead to unfavourable changes in the crystal lattice and ultimately destabilisation of the perovskite phase. Here we study the nanoscale early-stage degradation of mixed-halide mixed-cation perovskite films under operation-like conditions using electrical scanning probe microscopy to investigate the formation of surface nanograin defects. We identify the nanograins as lead iodide and study their formation in ambient and inert environments with various optical, thermal, and electrical stress conditions in order to elucidate the different underlying degradation mechanisms. We find that the intrinsic instability is related to the polycrystalline morphology, where electrical bias stress leads to the build-up of charge at grain boundaries and lateral space charge gradients that destabilise the local perovskite lattice facilitating escape of the organic cation. This mechanism is accelerated by enhanced ionic mobility under optical excitation. Our findings highlight the importance of inhibiting the formation of local charge imbalance, either through compositions preventing ionic redistribution or local grain boundary passivation, in order to extend operational stability in perovskite photovoltaics.
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Curved X-ray detectors have the potential to revolutionize diverse sectors due to benefits such as reduced image distortion and vignetting compared to their planar counterparts. While the use of inorganic semiconductors for curved detectors are restricted by their brittle nature, organic-inorganic hybrid semiconductors which incorporated bismuth oxide nanoparticles in an organic bulk heterojunction consisting of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl C71 butyric acid methyl ester (PC70 BM) are considered to be more promising in this regard. However, the influence of the P3HT molecular weight on the mechanical stability of curved, thick X-ray detectors remains less well understood. Herein, high P3HT molecular weights (>40 kDa) are identified to allow increased intermolecular bonding and chain entanglements, resulting in X-ray detectors that can be curved to a radius as low as 1.3 mm with low deviation in X-ray response under 100 repeated bending cycles while maintaining an industry-standard dark current of <1 pA mm-2 and a sensitivity of ≈ 0.17 µC Gy-1 cm-2 . This study identifies a crucial missing link in the development of curved detectors, namely the importance of the molecular weight of the polymer semiconductors used.
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Controlling the radiative properties of monolayer transition metal dichalcogenides is key to the development of atomically thin optoelectronic devices applicable to a wide range of industries. A common problem for exfoliated materials is the inherent disorder causing spatially varying nonradiative losses and therefore inhomogeneity. Here we demonstrate a five-fold reduction in the spatial inhomogeneity in monolayer WS2, resulting in enhanced overall photoluminescence emission and quality of WS2 flakes, by using an ambient-compatible laser illumination process. We propose a method to quantify spatial uniformity using statistics of spectral photoluminescence mapping. Analysis of the dynamic spectral changes shows that the enhancement is due to a spatially sensitive reduction of the charged exciton spectral weighting. The methods presented here are based on widely adopted instrumentation. They can be easily automated, making them ideal candidates for quality assessment of transition metal dichalcogenide materials, both in the laboratory and industrial environments.
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Ferroelectric materials exhibit a phase transition to a paraelectric state driven by temperature - called the Curie transition. In conventional ferroelectrics, the Curie transition is caused by a change in crystal symmetry, while the material itself remains a continuous three-dimensional solid crystal. However, ferroelectric polymers behave differently. Polymeric materials are typically of semi-crystalline nature, meaning that they are an intermixture of crystalline and amorphous regions. Here, we demonstrate that the semi-crystalline morphology of the ferroelectric copolymer of vinylidene fluoride and trifluoroethylene (P(VDF-TrFE)) strongly affects its Curie transition, as not only a change in crystal symmetry but also in morphology occurs. We demonstrate, by high-resolution nanomechanical measurements, that the semi-crystalline microstructure in the paraelectric state is formed by crystalline domains embedded into a softer amorphous phase. Using in situ X-ray diffraction measurements, we show that the local electromechanical response of the crystalline domains is counterbalanced by the amorphous phase, effectively masking its macroscopic effect. Our quantitative multi-scale characterisations unite the nano- and macroscopic material properties of the ferroelectric polymer P(VDF-TrFE) through its semi-crystalline nature.
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Nanoscale investigations by scanning probe microscopy have provided major contributions to the rapid development of organic-inorganic halide perovskites (OIHP) as optoelectronic devices. Further improvement of device level properties requires a deeper understanding of the performance-limiting mechanisms such as ion migration, phase segregation, and their effects on charge extraction both at the nano- and macroscale. Here, we have studied the dynamic electrical response of Cs0.05(FA0.83MA0.17)0.95PbI3-xBrx perovskite structures by employing conventional and microsecond time-resolved open-loop Kelvin probe force microscopy (KPFM). Our results indicate strong negative charge carrier trapping upon illumination and very slow (>1 s) relaxation of charges at the grain boundaries. The fast electronic recombination and transport dynamics on the microsecond scale probed by time-resolved open-loop KPFM show diffusion of charge carriers toward grain boundaries and indicate locally higher recombination rates because of intrinsic compositional heterogeneity. The nanoscale electrostatic effects revealed are summarized in a collective model for mixed-halide CsFAMA. Results on multilayer solar cell structures draw direct relations between nanoscale ionic transport, charge accumulation, recombination properties, and the final device performance. Our findings extend the current understanding of complex charge carrier dynamics in stable multication OIHP structures.
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Non-linear electrical properties of a (biological) tissue can be revealed by non-linear electrical measurements, which means that the applied stimulus itself affects the measurement. If resulting voltage-current plots exhibit pinched hysteresis loops, the underlying tissue may be classified as a memristor, a state dependent resistor. The aloe vera plant and apples have been found to be memristors. However, polarization processes on the electrodes are also non-linear and may affect the measurement. Apples and aloe vera conduct electrical current very well and it is likely that the recordings are actually dominated by the polarization impedance of the electrodes. Here, we study the non-linear properties of aloe vera and apples with two different measurement electrode types. Furthermore, we measured also on the extracted liquids from one aloe vera leaf and one apple, leading to similar results. We concluded, unlike previous studies on these subjects, that the memristive properties originate from electrochemical reactions on the electrodes rather than the apples or aloe vera themselves.
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Charge transport in organic semiconductors is strongly dependent on the molecular orientation and packing, such that manipulation of this molecular packing is a proven technique for enhancing the charge mobility in organic transistors. However, quantitative measurements of molecular orientation in micrometre-scale structures are experimentally challenging. Several research groups have suggested polarised Raman spectroscopy as a suitable technique for these measurements and have been able to partially characterise molecular orientations using one or two orientation parameters. Here we demonstrate a new approach that allows quantitative measurements of molecular orientations in terms of three parameters, offering the complete characterisation of a three-dimensional orientation. We apply this new method to organic semiconductor molecules in a single crystal field-effect transistor in order to correlate the measured orientation with charge carrier mobility measurements. This approach offers the opportunity for micrometre resolution (diffraction limited) spatial mapping of molecular orientation using bench-top apparatus, enabling a rational approach towards controlling this orientation to achieve optimum device performance.
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The performance of hybrid (organic-inorganic) photovoltaic devices is critically dependent on the thin film morphology. This work studies the film formation process using the in situ thermal decomposition of a soluble precursor to form a well-distributed network of CdS nanoparticles within a poly(3-hexylthiophene) (P3HT) polymer matrix. Resonant Raman spectroscopy is used to probe the formation of the inorganic nanoparticles and the corresponding changes in the molecular order of the polymer. We find that the CdS precursor decomposes rapidly upon heating to 160 °C, but that this has a disruptive effect on the P3HT. The extent of this disruption can be controlled by adjusting the annealing temperature, and nanowire aggregates of P3HT are found to have increased susceptibility. Atomic force microscopy reveals that at high temperatures (>200 °C), cracks form in the film, resulting in a 'plateau'-like microstructure. In order to retain the preferable 'granular' microstructure and to control the molecular disruption, low decomposition temperatures are needed. This work identifies a particular problem for optimising the hybrid thin film morphology and shows how it can be partially overcome.
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Two semiconducting conjugated polymers were synthesized via Stille polymerization. The structures combined unsubstituted or (triisopropylsilyl)ethynyl (TIPS)-substituted 2,6-bis(trimethylstannyl)benzo[1,2-b:4.5-b']dithiophene (BDT) as a donor unit and benzotriazole with a symmetrically branched alkyl side chain (DTBTz) as an acceptor unit. We investigated the effects of the different BDT moieties on the optical, electrochemical, and photovoltaic properties of the polymers and the film crystallinities and carrier mobilities. The optical-band-gap energies were measured to be 1.97 and 1.95 eV for PBDT-DTBTz and PTIPSBDT-DTBTz, respectively. Bulk heterojunction photovoltaic devices were fabricated and power conversion efficiencies of 5.5% and 2.9% were found for the PTIPSBDT-DTBTz- and PBDT-DTBTz-based devices, respectively. This difference was explained by the more optimal morphology and higher carrier mobility in the PTIPSBDT-DTBTz-based devices. This work demonstrates that, under the appropriate processing conditions, TIPS groups can change the molecular ordering and lower the highest occupied molecular orbital level, providing the potential for improved solar cell performance.